Trisazo dyestuffs containing two carboxamide groups

ABSTRACT

WHEREIN A, K, B and M each denotes an aromatic residue, D and E each denotes an aromatic or heterocyclic residue and G denotes a hydrogen atom or an organic residue, the residues D and E-O-G being different from one another and the residues A-N N-B- and/or K-N N-M- containing groups which impart solubility in water.   This invention relates to new trisazo dyestuffs containing two acylamino groups and their use for the production of photographic materials, especially as image dyestuffs for the silver dyestuffs bleaching process. The trisazo dyestuffs of the invention are those of the formula

United States Patent [1 1 Froehlich et al.

1 1 TRlSAZO DYESTUFFS CONTAINING TWO CARBOXAMIDE GROUPS [75] Inventors:Alfred Froehlich, Mar1y-Le-Grand;

Hansrolf Loeffel. Bern, both of Switzerland [73] Assignee: Ciba-GeigyAG. Basel, Switzerland [22] Filed: Oct. 2, 1972 [2]] Appl. No.: 293,964

Related US. Application Data [63] Continuation of Scr. No. 798,792, Feb.12, 1969,

abandoned.

[30] Foreign Application Priority Data Feb, 15. 1968 Switzerland 2253/68Mar. 11, 1975 Primary Examinerl-1enry R. Jiles Assistant ExaminerRobertW. Ramsuer Attorney, Agent, or Firm.loseph G. Kolodny; Edward McC.Roberts; Prabodh l. Almaula [57] ABSTRACT This invention relates to newtrisazo dyestuffs containing two acylamino groups and their use for theproduction of photographic materials, especially as image dyestuffs forthe silver dyestuffs bleaching process. The trisazo dyestuffs of theinvention are those of the formula wherein A, K, B and M each denotes anaromatic residue, D and E each denotes an aromatic or heterocyclicresidue and G denotes a hydrogen atom or an or ganic residue, theresidues D and E-O-G being different from one another and the residuesA-N=NB and/or K-N=NM- containing groups which impart solubility inwater.

8 Claims, N0 Drawings TRISAZO DYESTUFFS CONTAINING TWO CARBOXAMIDEGROUPS This is a continuation, of application Ser. No. 798,792,f1ledFeb. 12, 1969, now abandoned.

The present invention provides new trisazo dyestuffs of formula whereinA, K, B and M each denotes an aromatic residue, D and E each denotes anaromatic or heterocyclic residue and G denotes a hydrogen atom or anorganaic residue, the residues D and E-OG being different from oneanother and the residues AN=N-B-- and- /or K-N=NM- containing groupswhich impart solubility in water.

Particularly valuable trisazo dyestuffs are those of formula wherein A KB and M each denotes an aromatic residue containing one or two rings, Dand E each denotes an aromatic residue containing one or two rings or aheterocyclic residue having five or six ring members and G denotes ahydrogen atom or an organic residue, the residues D and E -OG beingdifferent from one another and the residues A N=NB and/or K,N=NM,containing groups which impart solubility in water.

Trisazo dyestuffs of formula are of particular interest, wherein A K Band M each denotes a benzene or naphthalene residue, D denotes a benzeneor naphthalene residue or a heterocyclic residue having five or six ringmembers, especially a triazole residue, E denotes a benzene ornaphthalene residue and G, denotes a hydrogen atom or an alkyl groupcontaining one to five carbon atoms, and wherein A and K may eachcontain one to three acidic groups imparting solubility in water, B andM may each contain one acidic group imparting solubility in water. and Dand E,7 may each contain halogen atoms, alkyl, alkoxy or phenyl groups,the residue -OG, being bound to the azo group in the 1,2- or1,4-position and the residues D and E OG being different from oneanother.

These trisazo dyestuffs also include those derived from two identicalaminoazo dyestuff molecules, namely dyestuffs of formula wherein A B D Eand G have the abovementioned significance.

Yellow trisazo dyestuffs of formulae (1) to (4) preferably correspond tothe formula wherein A denotes a benzene or naphthalene residue which maybe substituted by halogen atoms, alkyl, alkoxy or nitro groups andcontains one to three sulphonic acid groups, B;, denotes a benzeneresidue which may be substituted by at most two halogen atoms or alkyl,alkoxy, hydroxyalkoxy, alkoxyalkoxy, acylamino, carboxyacylamino (forexample a residue of formula HOOC-CH -CH -CONH), carboxyalkyl, carboxyor phenoxy groups or denotes a naphthalene residue, and wherein D E andG, have the abovementioned significance.

The residues A, K, A K A K and A of formulae (1) to (5) may be forexample derived from the following amines:2-aminonaphthalene-4,8-disulphonic acid,Z-amino-6-nitronaphthalene-4,8-disulphonic acid, 2-

aminonaphthalene-S,7-disulphonic acid, 1-aminonaphthalene-3,o-disulphonic acid, 2-aminonaphthalene-4,6,8-trisulphonic acid, 1- aminobenzene-3,5-dicarboxylic acid, 1

-aminobenzene-2-sulphonic acid and l-aminobenzene- 2,5-disulphonic acid.

The residues B, M, B M B M and B of formulae (1) to (5) may for examplebe derived from the following amines: aminobenzene, l-amino-2- or -3-methylbenzene, l-amino-2,5- or -2,6-dimethylbenzene, 1-amino-2- or-3-methoxybenzene, 1-amino-2- ethoxybenzene,l-amino-2-B-hydroxyethoxybenzene,l-amino-2-,B-methoxyethoxy-S-methylbenzene,

1amino-3-acetylaminobenzene, l-amino-3-nbutyrylaminobenzene, l-amino-3-propionylaminobenzene, l-amino-3 isobutyrylaminobenzene,1-amino-3-acetylamino-6- methylbenzene, l-amino-3-proprionylamino-6-methylbenzene, l-amino-3-n-butyrylaminc-6- methylbenzene,l-amino-3-isobutyrylamino-6- methylbenzene, l-amino-2-acetylamino-5- 3l-amino-2-propionylamino-5- methylbenzene, l-amino-2-n-butyrylamino-S-methylbenzene, lamino-2-isobutyrlamino-5- methylbenzene,l-amino-2-methoxy-5-methylbenzene, l-amino-2-methyl-S-methoxybenzene,l-amino-3- chlorobenzene,l-amino-2chloro-5-methoxybenzene,

methylbenzene,

l-amino-2-methoxy-S-chlorobenzene, l-amino-3- glutaroylaminobenzene,l-amino-3- succinoylaminobenzene, l-amino-3- fumaroylaminobenzene,l-amino-2,5-

wherein R, denotes a hydrogen atom, a halogen atom, a nitro group or asulphonic acid group, R denotes a hydrogen atom, a halogen atom, or analkyl, alkoxy, hy droxyalkoxy or alkoxyalkoxy group having in each caseone to five carbon atoms in the alkyl residue, a phenoxy, hydroxyaceticacid, acetic acid or acylamino group wherein acyl represents the residueof an aliphatic carboxylic acid having one to five carbon atoms or of abenzene carboxylic, pyridine carboxylic, furane carboxylic or thiophenecarboxylic acid which may be substituted, or a carboxyacylamino groupwhich is derived from an aliphatic discarboxylic acid having one to fivecarbon atoms or from a benzene dicarboxylic, pyridine dicarboxylic,furane dicarboxylic or thiophene dicarboxylic acid which may besubstituted, R denotes a hydrogen atom, or an alkyl, alkoxy or acylaminogroup, wherein acyl has the significance given for the residue R Ddenotes a phenylene, naphthylene, tolu-.

ylene, anisoylene, chlorophenylene, furoylene, thienylene,imidazolylene, quinolylene or triazolylene residue, E denotes aphenylene, naphthylene, toluylene, anisoylene, quinolylene orpyrazolonephenylene residue and G denotes a hydrogen atom or a methyl orethyl group, the residues D and E OG being different from one another.

Preferred yellow dyestuffs for example correspond to the formula soar 1l wherein R denotes a chlorine atom, or a methyl, methoxy or acetylaminogroup, R denotes a hydrogen atom, or a methyl, methoxy, ethoxy orhydroxyethoxy group, R denotes a hydrogen atom or a methoxy group and Gdenotes a methyl group, the residues of formulae I R0 NHCO j and NHCO-@being different from one another, the NHCO- groups always being bound bytheir CO- residue in the 3- or 4-position and the G O residue beingbound to the benzene residue in the 2- or 4-'position to the azo bridge.

Amongst these dyestuffs, those of formula O-Ga and/or l Ob) wherein Xdenotes a halogen atom and D, E and G have the above significance.

The residues D, D D and D may for example be derived from the followingdiazo components: 3-aminobenzene-l-carboxylic acid,4-aminobenzene-lcarboxylic acid, 4-amino-3-methylbenzenel carboxylicacid, 3-amino-4-methylbenzenel carboxylic acid,3-amino-4-methoxybenzene-1- carboxylic acid, 3-amino-4-chlorobenzene lcarboxylic acid, 5-amino-2-chlorobenzenel carboxylic acid,4-amino-2-chlorobenzene-1- carboxylic acid,2-aminothiophene-5-carboxylic acid, 2-amino-5-furane-carboxylic acid,5-amino-l,2,4-

triazole-3-carboxylic rived from the following coupling components:l-hydroxybenzene-2-carboxylic acid, l-hydroxybenzene-S-carboxylic acid,l-hydroxybenzene-4-carboxylic acid, l-hydroxy-4-methylbenzene-2-carboxylic acid, l-hydroxy-5- methylbenzene-2-carboxylicacid, l-hydroxy-6- methylbenzene-2carboxylic acid, 1-hydroxy-4-chlorobenzene-2-carboxylic acid, l-hydroxy-S-methoxybenzene-Z-carboxylic acid, 1- hydr'oxynaphthalene-Z-carboxylicacid, l-phenyl-3- carbethoxy-S-pyrazolone-3-carboxylic acid, 5-hydroxyquinoline-6-carboxylic acid, 6- hydroxyquinoline-4-carboxylicacid, 5- hydroxypyridine-2-carboxylic acid, 1,2- or 2,3-

hydroxynaphthoic acid and S-chlorosalicylic acid.

The condensation may be effected according to known methods and may beadvantageously carried out in a polar solvent for example water orespecially a polar organic solvent for example dimethylformamide,diethylacetamide or N-methylpyrrolidone. It is also advantageous tocarry out the condensation in the presence of acid-binding reagents forexample tertiary amines or alkali metal carbonates. The condensation mayalso be carried out in solvents which themselves act as acid-bindingagents for example pyridine or N methylpyrrolidone already mentioned.

The aminoazo dyestuffs of formulae (10a and (10b) may be manufacturedaccording to known methods for example by combining a diazo compound ofan amino of'formula ANH or K-NH wherein A and K have the significancementioned, advantageously in an acid medium, with a monoamine of formulal-l-BNH or H-M--NH capable of coupling, wherein B and M have the abovesignificance.

The dicarboxylic acid dihalides of formula (11) may be manufactured bydiazotisation of an aminobenzene carboxylic or aminonaphthalenecarboxylic acid or of an aminoheterocyclic carboxylic acid or estersthereof, and coupling with a compound of formula H.E, wherein E has theabove-mentioned significance, if desired followed by alkylation of ahydroxyl group in the oand p-position in the residue E, and reaction ofthe azobenzene dicarboxylic acid thus obtained with a halogenatingagent, for example phosphorus pentachloride, phosphorus trichloride,thionyl chloride or phosgene, if desired in the presence of an ineertsolvent with or without the addition of, for example, pyridine ordimethylformamide as catalyst.

Another process for the manufacture of trisazo dyestuffs of formula (1)is characterised in that a diazonium compound of an amine of formulawherein A and B have the significance mentioned above is coupled with acompound of formula wherein E, M and K have the significance mentionedabove and G represents a hydrogen atom.

The diazonium compounds of the amines of formula (12) can be obtained invarious ways. Either a carboxylic acid halide of formula (14) X-O Owherein X has the significance already mentioned, is condensed with acompound of formula (10a) and/or (10b), the nitro group reduced to theamino group and diazotised, or a carboxylic acid halide of formula (15)XO C wherein X has the significance already mentioned and Y representsthe residue -NHZ or N=Z, wherein Z represents a removable protectivegroup, is condensed with a compound of formula (10a) and/or (10b), theprotective group split off and the amino group diazotised. Suitableprotective groups are for example phthaloyl, carbalkoxy, carbophenyloxy,carbobenzoxy or triphenylmethyl groups.

The compounds of formula (15) may be advantageously manufactured byreacting the derivatives of the aminocarboxylic acids with thedicarboxylic acid anhydrides or the reactive halogen compounds of theprotective groups in an aqueous-alkaline medium or in an inert solvent,if desired in the presence of compounds which add hydrogen halides forexample pyridine or triethylamine. After saponification and conversionto the carboxylic acid halide, preferably the chloride or bromide, thereaction with the aminoazo dyestuffs of formula (10a) and/or 10b) isthen carried out in the usual manner. The manufacture of products havingprotective groups and the splitting off of the protective groups underthe appropriate conditions are known from protein chemistry.

As examples of compounds from which suitable carboxylic acids and theirderivatives may be derived, the compounds of the following formulae forexample may be mentioned:

COOH $00K COOH COOH COOH NO NOz NO2 -CH3 NO; 1 N02 COOH om t NO2S/-COOII O CHa Using these manufacturing processes, three azo dyestuffresidues which may be different from one another can be combinedtogether in one melecule in a simple manner.

The trisazo dyestuffs of formula (1) can be used for various purposes,for example in the production of photographic materials and particularlyadvantageously as image dyestuffs for the silver dyestuff bleachingprocess. Valuable photographic materials which contain at least onelayer having a dyestuff of formula (1) on a support can accordingly bymanufactured in the usual manner by known methods.

In particular, the trisazo dyestuffs may be present in a multi-layermaterial which on a layer support contains a layer which is dyed with agreenish-blue dyestuff and is selectively sensitive to red, over this amagentacoloured layer which is selectively sensitive to green andfinally a yellow-coloured layer which is selectively sensitive to blue.

The trisazo dyestuffs of formula (1) can be used in the various layers.

The dyestuffs of formulae (5) (6), (7) and (8) are particularly suitablefor the layer which is sensitive to blue in a silver dyestuff bleachingprocess.

The dyestuffs of formula (1) may also be incorporated into an auxiliarylayer or especially into a layer adjacent to the light-sensitive layer.

The dyestuffs of formula (1) are very diffusionresistant in the usuallayers. They do not tend to change to an opalescent to cloudly form ingelatine layers on drying and storage. and they can be readily reducedin the bleaching bath to form harmless and/or easily washed-outdecomposition products.

The dyestuffs of formula (1) are distinguished by particularly highcolour strength and purity of shade. Grey shades which appear neutral tothe eye over the entire density range can be produced with them, forexample by combining a yellow dyestuff of formula (7) or (9) with oneeach of a suitable magenta and cyan dyestuff.

Compared to other trisazo dyestuffs, the dyestuffs of formula (1) arequite exceptionally distinguished by their good solubility andcompatibility with cations, especially calcium ions. They arenevertheless extraordinarily diffusion-resistant over a pH range of -11.

In many cases it is particularly difficult to displace the absorption ofyellow dyestuffs by small amounts, for example by nm towards longerwavelengths, or to flatten an excessively steep flank of the absorptioncurve, particularly in the direction of longer wavelengths, as can undercertain circumstances be desirable to produce a neutral grey shade, whenappropriately combining all three dyestuffs, over all density ranges.

The present invention therefore also provides photographic material,especially for the silver dyestuff bleaching process, which contains ona support, at least one layer having a dyestuff of one of formulae (1)to (7) and '(9).

Percentages given in the manufacturing examples which follow arepercentages by weight.

EXAMPLE 1 1.1. 2-Aminonaphthalene-4,8-disulphonic acid is diazotised inthe usual manner and coupled with 2- methoxy-S-methylaniline.

1.2. p-Aminobenzoic acid ethyl ester is diazotised in the usual mannerand coupled with salicylic acid methyl ester. A yellow azo dyestuff isobtained which melts at 151 C after recrystallisation from acetone.

The hydroxyl group of this dyestuff is methylated in the usual mannerwith dimethyl sulphate in acetone in the presence of potassiumhydroxide. The resulting methylation product melts at 140 C.4-Methoxyazobenzene- 3,4'-dicarboxylic acid of melting point 275 to 278C is obtained by saponification of the two ester groups. 400 g of thisacid are dissolved in 400 ml of toluene and 63 ml of dimethylformamideat C, mixed at room temperature with 245 ml of thionyl chloride, and thetemperature is raised to C in 1 hour. The mixture is stirred for afurther 2 hours at 90 C, filtered hot and the filtrate slowly allowed tocool to 0 C. The mixture is filtered and the residue washed three timeswith 300 ml of petroleum ether each time.

430 g of yellow needles of melting point 138 C are obtained.

1.3. 5.40 g of the product manufactured according to 1.1. are dissolvedin 44 ml of N-methylpyrrolidone at 120 C. The mixture is then cooled to80 C, 1.50 ml of dry pyridine are added and 2.50 g of the productmanufactured according to 1.2. are introduced whilst stirring. Theaddition of the product according to 1.2. is continued until no furtherproduct according to 1.1. can be detected chromatographically in thereaction mixture. The stirrer and the heating are then switched off andthe mixture is slowly allowed to cool to room temperature. The yellowcrystals which have separated are filtered and washed with 2.00 ml of N-methylpyrrolidone. The residue is boiled with 50 ml of methanol for 1hour whilst stirring, filtered and washed three times with 2.50 ml ofmethanol each time. The

residue is then boiled for one hour with 40 m1 of metha- 80 K OCH;

C Ha

2.1. p-Aminobenzoic acid ethyl ester is diazotised in the usual mannerand coupled with p-hydroxybenzoic acid methyl ester. A yellow dyestuffof melting point 123 C is obtained. The hydroxyl group of this dyestuffis methylated in the usual manner with dimethyl sulphate in acetone inthe presence of potassium hydroxide. The methylation product has amelting point of 153 C after recrystallisation from percent acetic acid.The ester groups are saponified with sodium hyroxide and thesaponification product is crystallised from dimethylformamide. The acidhas a melting point of 305 to 308 C.

4 g of this acid are suspended in 6.7 ml oftoluene and after adding 3drops of dimethylformamide are mixed with 4 g of thionyl chloride. Thereaction mixture is then warmed to 100 C whilst stirring. After 10 allthe material dissolves. The mixture is heated for a further 20 minutesto 100 to 105 C, a further 6.7 ml of toluene are added and the mixtureis allowed to cool slowly. The product is filtered, washed with 20 ml ofpetroleum ether and crystallised from 30 ml of benzene. 3 g of the acidchloride of melting point 120 C are obtained.

2.2. 5.4 g of the yellow dyestuff manufactured according to 1.1. aredissolved in 44 ml of N- methylpyrrolidone at 120 C. The solution isallowed to cool to 80 C and 1.5 ml of pyridine are added. 2.5 g of theproduct according to 2.1. are then introduced with good stirring. Theaddition of the acid chloride according to 2.1. is continued until nodyestuff 1.1. can be detected chromatographically in the reactionmixture. The clear reaction solution is mixed with 150 ml of acetone,filtered, and the residue washed with 50 ml of acetone. The residue isboiled with 50 ml of methanol for 1 hour whilst stirring, filtered hotand washed three times with 20 ml of methanol each time. The residue isboiled for 1 hour with 40 ml of methanol and 6 ml of 20 percentalcoholic potassium acetate solution, filtered hot and washed four timeswith 10 ml of methanol each time.

2.7 g of the yellow dyestuff B of formula solK min s onc CIHa 5103K(|3ONII -N:N Z O 0011a (ion: K

are obtained.

EXAMPLE 3 3.1. 2-Methoxyaniline-S-carboxylic acid methyl ester isdiazotised in the usual manner and coupled with salicylic acid methylester. The resulting dyestuff is methylated with dimethyl sulphate inknown manner in acetone in the presence of potassium hydroxide and thetwo carboxyl groups are then saponified.

3.3 g of the resulting dyestuff are suspended in 20 ml of benzene andmixed with 5 g of phosphorus pentachloridc. The mixture is heated to 80C for 1 hour, allowed to cool to room temperature, and the resultingyellow crystals are filtered. washed with 3 ml of henzene and 20 ml ofpetroleum ether.

Yield: 2.1 g; melting point: 165" c. C.

3.2. 8 g of the product manufactured according to 1.1. are dissolved in60 ml of N-methylpyrrolidone and 10 ml of pyridine at 120 C then mixedat 80 C with 4 g of the product manufactured according to 3.1. Theaddition of the product according to 3.1. is continued until no productmanufactured according to 1.1. can be detected chromatographically inthe reaction solution. The reaction solution is then mixed with 300 m1of acetone, andthe product is filtered and washed three times with 50 mlof acetone each time. The residue is boiled with 100 ml of methanol and10 ml ofa percent solution of potassium acetate in methyl alcohol for 1hour, filtered and washed three times with 50 ml of methanol each time.

6 g of the yellow dyestuff C of formula K OCH:

I O CH:

l O CH:

are obtained.

EXAMPLE 4 4.1. 2-Aminonaphthalene-4,8-disulphonic acid is diazotised inthe usual manner and coupled with 2-[3 hydroxyethoxy-5methylaniline.

4.2. 5.5 g of the dyestuff manufactured according to 4.1. are dissolvedin 44 ml of N-methylpyrrolidone at C, mixed with 1.5 ml of pyridine, and2.5 g of the product according to 1.2. are introduced into this solutionat 80 C. The addition of product according to 1.2. is continued until noproduct according to 4.1. can be detected chromatographically in thereaction solution. The mixture is then allowed to cool slowly to roomtemperature and the product is filtered, rinsed with 10 ml ofN-methylpyrrolidone and the residue boiled with 50 ml of alcohol for onehour whilst stirring. 1t is'then filtered and the residue washed threetimes with 25 ml of alcohol each time. The residue is again boiled for 1hour with 40 ml of methanol with the addition of 6 ml of 20 percentpotassium acetate solution, filtered and washed three times with 10 mlof methanol each time.

4.6 g of the yellow dyestuff D of formula so K o CIIQCIIQOII N=N j m.N:N

11; tom

C -OCH3 O CHzCHzOH $03K o ONH N=N fills are obtained. 803K F. X A M PLE5 5.1. 2-Aminonaphthalenc-4,8'disulphonic acid is diazotised in theusual manner and coupled with 3-npropionylaminoaniline.

5.2. 1.0 g of the dyestuff according to 5.1. is dissolved in 20 ml ofN-methylpyrrolidone at room temperature and 0.35 g of the productaccording to 1.2. are introduced into this solution. The addition ofproduct according to 1.2. is continued until no product according to5.1. can be detected chromatographically in the reaction solution. Thedyestuff formed is precipitated by adding 200 m1 of acetone, filtered,the residue dissolved in 50 m1 of water and the dyestuff precipitatedwith potassium acetate, filtered and washed three times with 5 ml ofmethanol each time.

0.6 g of the yellow dyestuff E of formula 1001120113 503K (30 CIIQCIIZ!cm NH $03K (JO-NH K0; is obtained.

EXAMPLE 6 6.1. 2-Aminonaphthalene-4,8-disulphonic acid is diazotised inthe usual manner and coupled with 5-chloro-2-methoxyaniline.

6.2. A procedure analogous to 5.2. is followed and 0.6 g of the yellowdyestuff F of formula EXAMPLE 7 7.1. 2-Aminonaphthalene-4,S-disulphonicacid is diazotised in the usual manner and coupled with 2-methoxy-S-methylaniline.

7.2. p-Aminobenzoic acid is diazotised in the usual manner and coupledwith salicylic acid.

44.8 g of the resulting dyestuff are suspended in 90 ml of benzene, andmixed with 58 ml of thionyl chloride and l 1.2 ml of dimethylformamide.The mixture is heated to 55 to 60 C for 1 hour; a clear solution isproduced. This is allowed to cool and hydrochloric acid gas and sulphurdioxide are removed from the reaction solution by pumping the reactionvessel to 16 mm Hg for 1 hour. The residue is stirred with a mixture of30 ml of benzene and 70 ml of petroleum ether, filtered, pressed, washedwith a mixture of 25 ml of benzene and 75 ml of petroleum ether andimmediately further processed.

7.3. 7 g of the dyestuff manufactured according to 7. I. are dissolvedin 70 ml of N-methylpyrrolidone and 7 ml of pyridine at 70 C and theacid chloride obtained from 7.2. is slowly added at this temperature,the'progressive condensation being checked during theaddition by thedisappearance of the amino group which is recognisable by diazotisationand coupling in a spot test. When no further amino group can bedetected, the reaction solution is stirred into 200 ml of acetone andthe dyestuff which has separated is filtered and twice washed with 100ml of acetone each time.

The residue is boiled with 50 ml of methanol and 5 ml of a 20 percentsolution of potassium acetate in methyl alcohol for 10 minutes, filteredand washed three times with 50 ml of methanol at 60 C.

5 g of dyestuff G of formula are obtained.

EXAMPLE 8 8.1. 2-Aminonaphthalene-4,8-disulphonic acid is diazotised inthe usual manner and coupled with 3- succinylaminoaniline.

8.2. 3 g of finely powdered dyestuff according to 8.1. are suspended in60 m1 of N-methylpyrrolidone and 5 ml of pyridine and this suspension ismixed at C with 2 g of 4-methoxy-azobenzene-3,4'-dicarboxylic aciddichloride (manufactured according to example 1.2.). Acid chloride isadded until no further amino group is detectable after diazotisation andcoupling in a spot test. The reaction solution is stirred into 300 ml ofacetone, and the dyestuff which has separated out is filtered and washedthree times with 50 ml of acetone each time. The residue is suspended inml of methanol; 2.5 ml of a 20 percent solution of potassium acetate inmethyl alcohol are then added, the mixture is boiled for 15 minutes, theproduct is filtered hot and washed three times with 50 ml of methanoleach time at 60 C.

1.6 g of the dyestuff H of formula K O a S NH coomomcoorr 0 ;K

s 03K N=NQO CH.

ONH-QN=N NH 03K co cmcaicoorr are obtained.

EXAMPLE 9 9.1. 2-Methoxyaniline-5-sulphonic acid is diazotised in knownmanner and coupled with 2-methoxy-5- methylaniline.

9.2. 6 g of the dyestuff according to 9.1. in 60 ml ofN-methylpyrrolidone and 3 ml of pyridine are heated to 80 C and mixedwith 2 g of 4-methoxyazobenze'ne- 3,4'-dicarboxylic acid dichloride(manufactured according to example 1.2.). Acid chloride is added untilno further amino group is detectable by diazotisation and coupling in aspot test.

The reaction solution is stirred into 300 ml of acctone and the dyestuffis filtered and washed three times with 50 ml of acetone each time.

The residue is suspended in 100 ml of methanol, ml of a 20 percentsolution of potassium acetate in methyl alcohol are added, the mixtureis boiled for 15 minutes, the product is filtered hot and washed at 60 Cthree times with 50 ml of methanol each time.

6.1 g of the dyestuff I of formula are obtained.

EXAMPLE 10.1. 2-Aminonaphthalene-4,8-disulphonic acid is diazotised inthe usual manner and coupled with laminonaphthalene.

10.2. 6 g of the dyestuff according to 10.1. are suspended in 100 mlofmethylpyrrolidone and 6 ml of pyridine, heated to 80 C and mixed with2 g of 4- methoxyazobenzene-3,4-dicarboxylic acid dichloride(manufactured according to example 1.2.). Acid chloride is added untilno further amino group is detectable by diazotisation and coupling in aspot test. The reaction solution is stirred into 800 ml of isopropanoland the product is filtered, washed with 300 ml of isopropanol and twicewith 100 ml of alcohol.

The residue is suspended in 100 ml of methanol, mixed with 20 ml ofa 20percent solution of potassium acetate in methyl alcohol, the solutionboiled for minutes, the product is filtered hot and washed with 100 mlof methyl alcohol.

4.8 g of the dyestuff J of formula stoic are obtained.

EXAMPLE 1 1 11.1. 2-Aminonaphthalene-4,8-disulphonic acid is diazotisedin the usual manner and coupled with 2- 14 methoxy-S-methylaniline.

l 1.2. p-Aminobenzoic acid ethyl ester is diazotiscd in the usual mannerand coupled with lhydroxynaphthalene-2-carboxylic acid methyl ester.

A yellow dyestuff of melting point 181 C is obtained.

1 1.3. 2.6 g of the dyestuff 11.2. are introduced into a mixture of mlof acetone and 2.8 g of powerded potassium hydroxide, the mixture isheated to 50C for 30 minutes, and 4.8 ml of dimethyl sulphate are thenadded during 15 minutes. The mixture is boiled for 3 hours, poured on tog of ice, mixed with 50 ml of 25 percent ammonia, filtered, and theresidue washed with water.

2.2 g of crude product are obtained and this is recrystallised from 600ml of alcohol and 1 g of charcoal. The resulting dyestuff has theformula (26) and melts at 138 C.

r-ntaooo-O-rwrw CO OCH:

OCH:

(I'OOII 11.5. 7.5 g ofthe dyestuff according to 11.4. together with 30ml of toluene, 1 ml of dimethylformamide and 8 g of thionyl chloride areheated to 100 C for 3 hours, whereupon the dyestuff dissolvescompletely. After cooling to 5 C the mixture is filtered and the residuewashed with 5 ml of toluene and with 50 ml of petroleum ether.

6 g of the acid chloride of formula (28), of melting point 178 C, areobtained.

11.6. 5 g of the dyestuff manufactured according to 11.1. in 50 m1 ofmethylpyrrolidone and 5 ml of pyridine are heated to 80 C and mixed atthis temperature with 3 g of the acid chloride according to 1 1.5. Theaddition of acid chloride is continued until no further amino group isdetectable by diazotisation and coupling in a spot test. The reactionsolution is then cooled to 20 C, stirred into 250 ml of acetone,filtered and the residue washed with 200 ml of acetone. The residue istaken up in 100 ml of methyl alcohol, mixed with 25 ml of a 20 percentsolution of potassium acetate in methyl alcohol, boiled for 15 minutes,filtered hot and washed with 100 ml of methyl alcohol.

5.2 g of the dyestuff K of formula 2g C0 C1 12.1.2-Amino-6-acetylaminonaphthalene4,8- disulphonie acid is diazotised inthe usual manner and coupled with 3-succinylaminoaniline.

12.2. 3 g of finely powdered dyestuff according to 12.1. are suspendedin 60 ml of N-methylpyrrolidone and 5 ml of pyridine and this suspensionis mixed at 80 C with 2 g of 4-methoxyazobenzene-3,4'-dicarboxylic aciddichloride. Acid chloride is added until no further amino group isdetectable by diazotisation and coupling in a spot test. The reactionsolution is stirred into 300 ml of acetone, filtered and the productwashed three times with 50 ml of acetone each time. The residue issuspended in 100 ml of methanol, mixed with 2.5 ml of a 20 percentsolution of potassium acetate in methyl alcohol, boiled for minutes,filtered hot and washed three times with 50 ml of methanol at 60 C eachtime.

1 omcrnooon 0O-CH;CH2COOH 03K are obtained.

EXAMPLE 13 13.1. 67 g of S-amino-l,2,4-triazole-3-carboxylic acid aresuspended in 300 ml of acetic acid/propionic acid 1:1, 200 ml of 37percent hydrochloric acid are added thereto, the mixture is cooled to 0C and 130 ml of 4N sodium nitrite solution are added in severalportions. Diazotisation is earriedout for 1 hour at 0 C.

The diazonium salt solution is poured into 80 ml of salicylic acidmethyl ester which have been diluted with 100 ml of methanol. The pH.value is raised from 3 to 9 by dropwise addition of 650 ml of 30percent sodium hydroxide solution. The mixture is stirred for 24 hoursat 0 tov 5 C. The intensely red-coloured suspension is heated to 50filtered, and the residue is recrystallised from 8,000ml of water.Yield: 71 g 48.8 percent of a yellow powder which decomposes above 260 Cand corresponds to the formula 13.2. 16 g of the intermediate product offormula (31) in 50 ml of H 0 and ml of 1 N sodium hydroxide solution arekept for 30 minutes at C. The mixture is cooled and adjusted to pH 7with concentrated hydrochloric acid. The product is filtered and washedwith a little water.

Yield: 5 g.

After crystallisation from ml of ethanol 3.5 g of a pale yellowchromatographically homogeneous product remain which decomposes at 270to 290 C and has the formula JOOH 13.3. 3.8 g of the intermediateproduct of formula (32) in 50 ml of thionyl chloride and 1 ml ofdimethylformamide are stirred for 1 hour at 50 to 55 C. Thereaftertheexcess thionyl chloride is evaporated in vacuo at 50 C. The acidchloride is then further processed for the manufacture of the requireddyestuff.

13.4. 7 g of the coupling product from diazotised 2-aminonaphthalene-4,8-disulphonic acid and 2- methoxy-S-methylaniline aredissolved in m1 of N- methylpyrrolidone and directly added to the acidchloride of 13.3. After 12 hours stirring at room temperature themixture is warmed to 60 C for 30 minutes and the dyestuff isprecipitated by adding 500 ml of acetone. The precipitated dyestuff isfiltered, the residue is dissolved in 30 ml of water, diluted with 300ml of methanol, and 5 ml of 7 N potassium acetate solution are added.The product is filtered and dried in vacuo at50 C.

Yield: 1.1 g of the orange dyestuff M of formula 14.1. 12.8 g of theintermediate product of formula (31) (91 percent content) are suspendedin 100 ml of dimethylformamide; 35 g of powdered potassium carbonate arethen added, followed after half an hour by 19 ml of dimethyl sulphate 26g). Foaming immediately starts with a slight rise in temperature.Thereafter the mixture is heated to 60 70 C for 5 minutes, and

100 ml of water and 2 N hydrochloric acid to give a pH of 7 are added todestroy the excess dimethyl sulphate. The reaction mixture is kept for 5minutes at 70 C and concentrated until a thick crystal sludge isobtained l7 l8 which is filtered, washed with 20 ml of methanol and Theabsorption maxima of dyestuff A to N dried in vacuo at 50 C. sured ingelatine, are listed in the table below. Yield: 4.5 g.

The product is purified by recrystallisation from 50 ml of ethanol and3.5 g of a yellow product of melting D point 152 to 165 c of the formulafi'fi A 423 (:14) Ill 2 N N 0 g 420 CmOOC JJ 4i-N= W -oc1n F G 4l2000011: T is: J 430 424 15 L 406 M 419 are obtained. N

14.2. 3.2 g of the intermediate product of formula (34) in 40 ml of l Nsodium hydroxide solution are heated to 90 C for minutes. The mixture isthen 20 EXAMPLElS neutfallsed with hydrqchloric acid i the precipi' Thefollowing layers are successively applied to an F filtered It dred vacuoat opaque white acetate film provided with an adhesive Y1eld: 1.4 g of ayellow powder wh1ch decomposes layer. above 300 C havmg the formula 5 1.Silver bromide emulsion in gelatine, sensitive to red, containing thegreenish-blue dyestuff of formula l4.3. 1.2 g of the intermediateproduct of formula 35 (35) in 30 ml of thionyl chloride and 1 ml ofdimethylformamide are stirred for 60 minutes at to C. The mixture isheated to reflux temperature for a short time and the excess thionylchloride is evaporated in vacuo. The resulting acid chloride is thenfurther pro- Cessed as follows- 2. Colourless gelatine layer withoutsilver halide.

g of the p i prodllct m dlazotlsed 3. Silver bromide emulsion ingelatine, sensitive to 2'3mmonaphthalene4,s'dlsulphonlc acld and green,containing the magenta dyestuff of formula methoxy-S-methylaniline aredissolved in 50 ml of N- methylpyrrolidone and directly added to theacid chlo 45 ride of 14.3. After 12 hours stirring the mixture is NH2heated to 50 C, kept for 30 minutes at this temperal N1tture and thenfiltered, and the filtrate is precipitated by I IH adding 500 ml ofacetone. The mixture is filtered, the 50 residue is dissolved in 30 mlof hot water and diluted with 300 ml of ethanol, and 5 ml of 7 Npotassium ace- H038 tate solution are added. The product is filtered anddried in vacuo at 50 C. 1I2

COHN c Yield: 0.8 g of the yellow dyestuff N of the formula G I O H SO HHO S 0 3k CH3 Ill N a 4. Yellow filter layer containing the dycstuff offormulu is developed in accordance with the following instruc-' trons:

l. 6 Minutes development in a bath which in one litre of water contains50 g of anhydrous sodium sulphate, 0.2 g of l-phenyl-3-pyrazolidone, 6 gof hydroquinone, 35 g of anhydrous sodium carbonate, 4 g of potassiumbromide and 0.3 g of benztriazole;

2. 5 minutes soaking;

3. 6 minutes fixing in a solution of 200 g of crystalline sodiumthiosulphate and 20 g of potassium metabisulphite in 1 litre of water;

4. 5 minutes soaking;

5. 3 to 12 minutes colour bleaching with a solution which in one litreof water contains 50 to 80 g of potassium bromide, 40 to 80 g ofthiourea, 35 to 80 g of 30 percent sulphuric acid and if desired 0.01 gof 2-amino- 3-oxyphenazine;

6. minutes soaking;

7. 5 minutes bleaching of residual silver with a solution of 60 g ofcrystalline copper sulphate, 80 g of potassium bromide and 15 ml of 30percent hydrochloric acid per litre of water;

8. 5 minutes soaking;

9. 5 minutes fixing as specified under 3;

l0. 5 minutes soaking.

The resulting positive image for viewing in reflected light is fast toslight and of the permanence required for documents.

Instead of dyestuff A, dyestuffs B to N can also be used with equallygood results.

We claim:

1. A trisazo dyestuff of the formula wherein R denotes hydrogen,halogen, nitro or sulphonic acid, R denotes hydrogen, chlorine, alkyl,alkoxy, hydroxyalkoxy, alkoxyalkoxy in each case having one to fivecarbon atoms in the alkyl moiety, phenoxy, hydroxyacetic acid, aceticacid or acylamino where acyl represents alkanoyl having one to fivecarbon atoms or of benzoyl, or carboxyacylamino which is derived fromalkylene dioic acid having one to five carbon atoms, R is hydrogen,methyl or methoxy or acylamino in which acyl has the significance givenfor R D is phenylene, naphthylene, toluylene, anisoylene orchlorophenylene, E is phenylene, naphthylene, toluylene or anisoyleneand G is hydrogen, methyl or ethyl, the residues D and E OG beingdifferent from one another.

2. A trisazo dyestuff of the formula 3031f Ilka N:N N]1CO in sonr N ll NN=NNII- c o in which R, is chlorine, methyl, methoxy or acetylamino, Ris hydrogen, methyl, methoxy, ethoxy or hydroxyethoxy, R is hydrogen, ormethoxy and G is methyl, and

NHCO 1 and -NIICO--m being different from one another and each NHCObeing bound by -CO- to 3- or 4-position and the G O being bound to thebenzene in the 2- or 4' position to the azo bridge.

3. A trisazo dyestuff according to claim 2 of the formula N:N--Nll ()0sour l i 803K 1 15 1y N=N HNCO/\ in which R, is methyl

1. A TRISAZO DYESTUFF OF THE FORMULA
 1. A trisazo dyestuff of theformula
 2. A trisazo dyestuff of the formula
 3. A trisazo dyestuffaccording to claim 2 of the formula
 4. A dyestuff of the formula
 5. Adyestuff of the formula
 6. A dyestuff of the formula
 7. A dyestuff ofthe formula